Trisazo-dyestuffs



Patented Jan. 10, 1950 UNITED STATES orF cE 2,493,975 ITmsAzo-DYEs'rUFFs Otto Kaiser, Dornacli, Switzerland, "assignorto CibaLimited, Basel, Switzerland ,aSwissfir n f No Drawing. Application May29, 1546, seams. 673,171. In Switzerland June 21,1945

In U. S. Patent Application Serial No. 480,371,

filed March 24, 1943, now Patent No. 2,435,356,

are described, inter alia, trisazo-dyestufls obtained by coupling adiazotized disazo-dyestufi of the general formula Ri-N=NR2--N=N-R3-NH2in which R1 represents the radical of an amino- 4 Claims. (Cl. 260-153)salicylic acid, and R2 and R3 represent the radicals of middlecomponents, with a derivative of a 2 amino5-hydroxynaphthalne '7sulfonicacid, of which the amino-group is connected directly orindirectly by means of a CO-orheterocyclic bridge to the radical of anaminosalicylic acid. The resulting dyestuffs, which yield on cellulosesuch as cotton or regenerated cellulose direct dyeings of very goodproperties of wet fastness after development with agents yieldingcopper, are characterized by the presence of two salicylic acidradicals.

' The present invention is based on the unexlpect'ed observation thattrisazo-dyestuffs, of which the dyeings can be after-treated with agentsyielding copper with equally good results,

"2 te'ristic atomic grouping of salicylic acid. Especially valuable arethe products in which both of the remaining halogen atoms have beenreacted in the aforesaid manner.

v; Ina modification of the above process the new dyestufis are made by'first coupling a diazocompound of a disazo-dyestufi of the abovegeneral formula with 2-amino-5-hydroxynaphthalene-'l-sulfonic acid in.such manner that coupling-occurs in the 6-position, which is broughtabout in-kno'wn manner-by conducting the reaction in a neutral oralkaline medium, and then causing the resulting trisazo-dyestuif toreact with a cyanuric halide and at least one aromatic amine oi-the kinddefined above; I

As dyestuffs of the general formula there come into consideration, forexample, dyestuffs of the following formulae notwithstanding that thedyestuffs contain only Q pling a diazo-compound of a disazo-dyestufl ofthe general formula in' which R1 represents a benzene nucleus con-'taining in 4-positi0n with respect to the N=N- 'l in kage a hydroxylgroup and in ortho-position 'with respect to the said hydroxyl group acar- I boxyl group, and, if desired, containing further 5 substituents,and R2 and R3 represent naphthalene nuclei in which the N=N- linkage andthe NHz group are in the 1 :4-p0sition relatively to one another, with acondensation'product of 1 molecular proportion of a cyanuric halide and1 one salicylic acid radical, can be obtained by coumolecular proportionof 2-amino-5-hydroxynaphthalene-'Z-sulfonic acid, in which condensationproduct at least one of the remaining halogen atoms has been reactedwith an aromatic amine -of thebenzene series not containing the charac-3 C O OH As aromatic amines which are caused to react with the tworemaining halogen atoms of the cyanuric halide there come primarily intoconsideration l-aminobenzene and its 3- or 4-su1fonic acid,

and derivatives thereof substituted in the nucleus the like.

Care must be taken so to select the various starting materials that thefinal products-contain, on theone hand, sufilcientssulfo groupsorcarboxyl groups to possess .adequate solubility,

and, on the other, not so many sulfo groups as to impair the dyeingcapacityandproperties of fastness of the final dyestufis. The *newdyestuffs may with advantage contain 3 sulfo groups,l-b.ut mayalternatively c0ntain'2 or 4 sulfo groups, of

which groups zone :01 twoare ,presentin the ,azo-

and one'or'two in'therconden'sed"aminonaphthol radical.

The new dyestufl's have:the general formula:

(V) "Rm-R4 in which R1, R2 and Rs have the meanings given above, R-irepresents .a-n aromatic nucleus of the benzene series, *which is freefromiHO-groups,

4 acid dissolved in 200 parts of water in the form of its sodium salt.The monoazo-dyestuff which separates is then brought into solution withaqueous caustic soda solution, mixed with 6.9 parts of sodium nitrite inthe form of a solution of 25 per cent. strength, and the mixture is runinto a mixture of 200 parts of ice-water and parts of concentratedhydrochloric acid.

The diazotization is conducted at 05 C. and when it is complete, thediazo-compound is precipitated by means of sodium chloride and thenseparated with suction. It is then coupled with 14.3 parts ofl-naphthylamine dissolved in 12 parts of concentrated hydrochloric acidand 150 parts of warm water. During the coupling 20 parts of sodiumacetate are strewn in, and the product is precipitatedafter ashort timeby the .addition .of sodium chloride. 'lIt.isbrought into solution witha small quantity of caustic soda .solution, mixed with 6.9 parts ofsodium nitrite in the form of a solution of 25 per cent. strength,

and the whole is diazotized at 15 C. with a mixture of 200 .parts ofice-water and 50 parts of concentratedhydrochloric acid. Thediazo-compoundis separated with suction, and then coupled with 58 partsof -the: ternary triazine condensation product obtained in known mannerfrom 1 molecular proportion of cyanuric chloride, 1 molecular proportionof 2-amino 5hydroxynaphthalene-7- sulfonic acid, 1 molecularproportionof l-aminobenzene-3-sulfonic 'acidand 1 fmolecular propor- 'tion ofaniline,'the said-condensation product bewing in a solution Tenderedalkaline with-sodium carbonate.

When coupling is finished *the dyestufi which corresponds in the. f-reestate .to ;.the formula .QsoiH -isseparated-and dried. -Itis a darkpowder which 'dyes cotton in a weakly-alkaline bath in thepresence ofcoppersulfate and sodium "tartrate grey tints which are fastto'washing.

[thylarriine-fl-sulfonic acid. Moreover, in the .ter-

tiary triazine condensation ,product 1 .molecular R5 representshydrogen'or alkyl, and "Ra repreproportionpf anilinemaybereplaced by =1molesents a halogen atom or the atomic grouping 7 *an 'aromatic radicalof the benzene series free from "hydroxyl groups. i

As compared withsimilar known dyestufis deacularg-propor-tion.of.N-monomethylaniline.

Ewample 2 coupled at .'0 .C; in presence .of .sodium .acetate with 22.3,parts of l-napthylaminea7=sulfonic .acid dissolved .in.the .formofitssodium saltin scribed in U. S. Patent NO. 2,215,087 and French 5 200parts ofvwaten 'TheIsgparatedfidyestufiismhen Patent No. 861,674, someoff the new dyestufis are distinguished by the considerably improved fastness to acid of their after-coppered dyeings.

The following examples illustrate the invention, v the p'arts being byweight: v

Ea'ample 1 153 parts of 1aamino 3-carboxy 4 hydroxybenzene arediazotized'imthe usual manner and V coupled at 0 C. in the presence ofsodium acetate brought-.- into solutionbymeansof aqueouscaustic sod-a:solution,. mixed .with..6.9 parts .ofsod-iumnitriteinh-me .form of anaqueous so1ution .-.of.25 per :cent. strength, and the wholeis allowedJim-run .into :a .mixture of .200 parts 10f ice-water and 50 "parts ofconcentrated hyd iochloricacid. When theaiiazotization, which is-carriedout :at--0-5-.C.,

is; finished, ;,-the diazoacompou-nd is precipitated.bmmeansoi;sodiuml-ehlcridesrseparatedaby:fiiterwith 22.3 parts of1-naphthylamine-7-sulfonic ing with suction, and coupled with a further22.3

wow

parts of i-naphthylamine-Fsulfonic acid disrepresent alkyl or hydrogen.Theatomic groupsolved in 200 parts otwater in the form of-. its ing Isalt. During the coupling 29,- of R; sodium acetate are strewn in, andthe product is precipitated after a short time with sodium chloride. Itis brought into solution with ajsmall R4 quantity of caustic sodasolution, mixed with 6.9 y, sgepresent,t -r f line, o parts of sodiumnitrite in the -form of a solution? monomethylanilinemf monoethylaniline, oijmoniof 25 per cent. strength, and the mixture is (1111-; e iyl'mcta-toluidinero n P 94- Oimetazotized at C. by means of a miXturQoi'2O9-" 6'"-toluidine, of ortho--:or para-anisidine or =pheneparts ofice-water and 50 parts of concentrated tidincr D metap -c n i t isanhydrochloric acid. The precipitated diazo c'om- Plies 80 0 the radicalpound is then coupled with 44.3 parts of tliel sec- .1 :v 3' ondary.triazine condensation product obtained in known manner irom 1.molecular proportion of 15 cyanuric chloride, 1 molecularproportion'i'of 2- a I p,

amino-5-hydroxynaphthalene 7 --su1foiiic acid .Moreover 4 n R5 may alsowntam a u and 1 molecular proportion of aminobenzehe',r the P- n he atcrc e the gr ps condensation product being in a solution rendered R;

alkaline with sodium carbonate. v and/or -When the coupling is finishedthe dyestufi, 4 I

which corresponds in the free state to tli e fory mula is separated anddried. It is a'dark powder represent the radicals of amino-sulfonicacids of /C\ N N Nat t HN which dyes cotton from a weakly alkaline baththe benzene series, such asrl-aminobenzene-iiin the presence of coppersuliateandsodium sulfonic acid, j l-aminobenzenel-sulfonic acid,tartrate grey tints which are fast to washing1-amino-2-me'thoxybenzene-4-su1fonic acid, 1- A similar dyestufi isobtained when l-napthylaamino-2-methylbenzene-5-sulionic acid,l-amimine-'Z-sulfonic acid is replaced once ortwiceno-4-methylbenzene-3-sulfonic acid and the by 1-naphthylamine-6-sulfonicacid or bya comlike. In the case of disazo-dyestufis which conmercialmixture of both acid'sfAdyestuft dying 40 tain only one sulfo-group,there are advantasomewhat greenish grey tints is obtained by geouslyused secondary or ternary condensation replacing in the presentexample'the secondary products which contain two sulfo-groups; but thetriazine condensation product by the tertiary use of condensationproducts having only one triazine condensation product of the firstparaa sulfo-group not excluded, For example, such graph of the foregoingExample 1. M secondary or ternary condensation products hav- Otherdyestuffs of the invention can be ob-i-M ing twosulio groups, such asthe product of the tained by the procedures described in theprecedformula ing Examples 1 and 2 with the aid of the diazocompoundsoi'the disazo-dyestufis of the Formulae I-'-IV hereinbefore given. Whenidisazodyestuifs which contain two sulfo-groups are chosen are startingdyestuffs, there are advantageously used as coupling componentssecondary s or ternary condensation products which contain only one orat most two sulfo-groups, that is to say compounds of the generalformula N--R| I 0o or hay ing a singleisulfo-group such as the product1/ of theiormula Y; HOaS N (5 .(tx-R. 1 t

I, tY

in which R8 represents halogen or a group N/ N R1 no n-hvt-N-o-oon. 11-11: 1!:

in which R4 and if desired Rs represent benzene nuclei, which are freefrom hydroxyl groups and of which at most one may contain not more than1 sulfa-group, and R5 and if desired Ba may be used.

Mae-m 1. A trisazo-dyestuff, capable of lized, of the formula beingmetak in which R1 stands for a member of the group consisting ofhydrogen and an alkyl radical, R2

for an aromatic nucleus of the benzene series free irom; hydnoigy andcafboxylicacid groups and 3c "fora member of the group consisting II-chlorine and the residue of an-aromatic 'amineof theflieh- .;3. I hetrisazo-dyes'tuff, capablenfbei ng meta 1- lized, of.the formula vREFERENCEEQPIIED" "gene series fiee 'immhydmxyanimarbokylicaciflifgrmips and '"limked wlth its nitrogen -atom to *th'e ftri alz'inering, in which further one a: represent's a sulfonic acid group and the1 other ande one represent mydrbgen atoms, -and:the.nther y -1'.ep1:e-.:sents1asmemberc ofithezgmup@consisting;.of hydrorgeman'd asulfoiaicwmcidlgroulp.

l 22. fiIhe irisazo-dyestufl, incapable of :heing251aallize'dmf'theiformula V The following references 'arewf. record-ii1the i elmwe l? when" s ra'rnfi PATENTS Number V Name" a 1,667,312Fritzche et a1 Apr. 24, 1928 1,788,295 Hentrich et a1 Jan. '6, 19312,084,731 Gyr et a1 June22, 1937 12,215,037 h ,fichweitze; Sept. 1'1,1940 2268319 .fihn'derali Jan.- 6,1942

2,270;6'7:5 'Stein et a1 Jan. 20, 1942 7 2,396,659 Kaiser Mar. 19, 1-946Certificate of Correction Patent No. 2,493,975 January 10, 1950 OTTOKAISER It is hereby certified that errors appear in the printedspecification of the above numbered patent requiring correction asfollows:

Column 3, line 33, for that portion of the formula reading R N read R N;column 5, line 22, strike out is separated and dried. It is a darkpowder, and insert the same before the word whic in line 34, samecolumn; lines 37 and 38, for l-napthylamine read I-naphthylamz'ne;

and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Ofiice.

Signed and sealed this 25th day of April, A. D. 1950.

THOMAS F. MURPHY,

Assistant Commissioner of PM.

1. A TRISAZO-DYESTUFF, CAPABLE OF BEING METALLIZED, OF THE FORMULA